Transparent polyamides from an isomeric mixture of norbornanes

ABSTRACT

Transparent polyamides are produced by polycondensing mixtures of isomeric amino-methyl amino-propyl norbornanes or mixtures thereof with aliphatic, cycloaliphatic, aromatic or aromatic aliphatic diamines and aliphatic, cycloaliphatic or aromatic dicarboxylic acids or mixtures of the said dicarboxylic acids with amino carboxylic acids.

United States Patent [191 Reske et al.

[4 1 July 15,1975

[73] Assignee: Hoechst Aktiengesellschaft,

Frankfurt am Main, Germany [22] Filed: Dec. 26, 1972 [21] Appl. No.: 317,943

[52] US. Cl. 260/78 R; 260/33.4 P; 260/65;

260/78 A; 260/78 L; 260/563 P [51] Int. Cl. C08g 20/20 [58] Field of Search 260/78 R, 78 L, 78 A [56] References Cited UNITED STATES PATENTS 3,301,827 1/1967 Martin 260/78 R 3,787,371 l/l974 Brinkmann et al. 260/78 R Primary Examiner-Harold D. Anderson Attorney, Agent, or FirmCurtis, Morris & Safford [5 7] ABSTRACT Transparent polyamides are produced by polycondensing mixtures of isomeric amino-methyl aminopropyl norbornanes or mixtures thereof with aliphatic, cycloaliphatic, aromatic or aromatic aliphatic diamines and aliphatic, cycloaliphatic or aromatic dicarboxylic acids or mixtures of the said dicarboxylic acids with amino carboxylic acids.

12 Claims, No Drawings 1 2 TRANSPARENT POLYAMIDES FROM AN droformylation of diolefins in the presence of rhodium ISOMERIC MIXTURE OF NORBORNANES or cobalt in finely distributed formor compounds of rhodium or cobalt in the known manner and subse- The present invention relates to transparent polyamquent catalytic-reductive amination of the mixture of ides and to a process for their preparation. dialdehydes obtained. As diolefin 2-vinylor Polyamides prepared from aliphatic diamines and di- 2-ethylidene-norbornene-S 01' a mixture Of these diolecarboxylic acids h ve b n k w f r a l n tim N fins is used, and the catalytic reductive amination is carried out in such a way that ammonia, hydrogen, catalyst and optionally a solvent are introduced into the high-pressure vessel and only when the reaction temperature is reached the dialdehydes are pumped in while stirring, quickly enough for them to be immedimerous polyamides are crystalline. The crystalline products cannot be used anywhere where transparency is necessary. Other polyamides are amorphous. Their melting point is relatively low and they have low second order transition temperatures. These polyamides lend themselves well to sheets, strips, plates, tubes, wire covately feductively amihatederings and to various injection molding articles. How- The reactions taking place when starting with ever, they can only be used at low temperatures on acl5 2-vinyl-nor men -5 (formula I -e hy iden count of their low second order transition temperan0rbornen-5(Formula IV tures, which, greatly limits their usefulness.

A process for the preparation of polyamides by polyl condensation of diamines and dicarboxylic. acids or 6 their amideforming derivatives in the known way and under the usual conditions has now been found, which 5 3 t I I I l I V comprises using: 4

a. mixtures of isomeric amino-methyl-aminopropylnorbomanes of the formulae l are illustrated as follows, using a compound of formula Ill 2 2 3 and 3 I 4 R l 4 cs0 I +2CO+2H, 0HC

CH0 CH NH OHC- 2 H 2 NH, HZNCHZ i whi 1 iS all amine m hyl-(NH2- H2)-r ical Mixtures of 4 isomeric aminomethylaminopropylnorand R 21 bornanes of the general formulae CH3 l-aminopropyl-2-(CH )-radical 1 R 2 R 2 cmNl-n (I I) or a 3-aminopropyl-I-(CH2CH2CH NH2) (I and radical, or-mixtures of the isomeric diamines named R with one or several further diamine(s), these being 1 aliphatic or cycloaliphatic diamine(s) with 2 to 20, are obtained, wherein R and R have the abovepreferably 2 to 12,carbon atoms or aromatic diamine(s) defined gwith 6 to 20, preferably 6 to 15, carbon atoms, above It has been found y gas chromatographic analysis all mononuclear diamine(s) of the benzene series, or that when using 2-ethyhdehe-h01'h0mene-5 the Same aromatic aliph tic di i i h 7 to 20 carbon mixtures of diamines are obtained as when using atoms d 2-vinyl-norbornene-5, ie. 2-vinyl-norbornene-5 is formed at the beginning of the reaction from b. one ofseveral dic rbox lica 'd ,th b I l'- a y cl (S) ese 6mg 3 l Z-ethyhdene-norbomene-S by isomerization.

phatic or cylcoaliphatic dicarboxylic acid(s) with 2 to 20, preferably 2 to 12, carbon atoms, or aromatic divinylnorbomeneaormula In) is easily accessible carboxylic acid(s) with 7 to 20,preferably s to 15, carfrom cyclopemadiene and butadiene y Dials-Alderbon atoms, above all mononuclear dicarboxylic acid(s) Synthesis Ethyhdehe nol'bomehe (Formula can be f h benzene series, obtained likewise in the known way from vinylnorboror mixtures of the dicarboxylic acids named with one hens through isomerization of the double bond of the or several aminocarboxylic acid(s) with 2 to 20, prefer- Vinyl groupably 2 to 12, carbon atoms, above all w-aminocarboxy- The hydroformylization of these two compounds lic acid(s) or (their) lactam(s) with a mixture of C0 H (synthesis gas) can be car- The mixture of isomeric diamines of the formulae I ried out in the known way in the presence or absence and II (aminomethyl-aminopropyl-norbomanes, bisof a solvent at atemperature of from to C and (aminomethyl)-2-ethyl norbonanes) required for the at a pressure of from 100 to 1,000 atmospheres gauge preparation of the polyamides of the invention can be or more. When using cobalt catalyst the reaction prepared from the inexpensive starting materials by hyshould preferably be carried out at a temperature of from 140 to 170C and ma pressure of from 150 to 400 atmospheres gauge; forrhodium catalysts ranges of from 1 10 to 140C and=l50 to'600 atmospheresgauge are advantageous. H I Aliphatic or :aromatic hydrocarbons aree'specially suitable as solvents; preferably ,mononuclear aromatic hydrocarbons suchas benzene or toluene are used.

Catalysts suitable for the reaction are the carbonyls of rhodium and cobalt, carbonyl forming compounds of these metals or the elements in finely distributed form.

Carbonyl-forming compounds of rhodium which arepreferred are dirhodiumtrioxide and the Rh-salts of weak acids such as acetic acid or 2-ethylhexanoic acid. The rhodium concentration can vary between 10 and 10' g-atom rhodium/mol diolefin, the preferred range being between 10 and g-atoms Rh/mol diolefin. The cobalt concentration can be between 10 and 10' g-atom CO/mol diolefin, the preferred range being 5 10 to 10 g-atom CO/mol diolefin.

Rhodium carbonyl compounds are preferable as catalysts because in comparison to the corresponding compounds of cobalt they produce a better yield of dialdehydes at considerably lower catalyst concentrations.

The working up of the dialdehydes takes place expediently by film distillation at pressures of under 40 mm Hg, preferably under 10 mm Hg, and heating jacket temperatures of up to 200C.

Dialdehydes condense very easily with ammonia into polymeric products. Also the dialdehydes obtained from vinylnorbornene or ethylidene norbornene react under conditions with which no hydrogenation'occurs, for example because the temperature is too low, with ammonia to polymeric solid products which subsequently cannot be converted into diamines any longer. These useless condensation products occur even at temperatures below 0C.

The process described above and in the following makes it possible to convert the dialdehydes nevertheless with good yields into the isomeric aminomethylaminopropyl-norbornanes. The catalytic-reductive amination is carried out in such a way that ammonia, hydrogen, catalyst and optionally a solvent are placed in the .high pressure vessel and at the reaction temperature tlie dialdehydes are pumped in while stirring, at a rate so that they are aminated reductively immediately.

The reaction is carried out expediently at temperatures of from 100 to 160C, preferably 120 to 150C. The hydrogen pressure in the reaction vessel is set at room temperature at 100 to 180 atmospheres gauge; during the heating the pressure increases considerably;

when the reaction temperature has been attained, a

total pressure of 200 to 320 atmospheres gauge is reached.

Nickel or cobalt are used as hydrogenation catalysts,

either in the form of Raney-nickel or Raney cobalt or applied on carriers. Preferably a catalyst containing approx. 45% cobalt on kieselguhr is used.

Ammonia should be used in excess; per mol of formyl group preferably atleast 2 mols of ammonia are necessary, more preferably4 to 5 mols of ammonia are used.

The reduction amination of the dialdehydes can be carried out without special solvents, possibly the end product itself can'be used as solvent. 1n the case of small discontinuous b'atches it is, however, advantageous to work in suitable solventsuEs'pecially good results are obtained when using tetrahydrofurane, isobuverted into higher molecular condensation products.

These condensation products are solids, but fluid, under the specified conditions and reaction mixture,

- which ,is very advantageous for a simple product withdrawal from the reactor and a working up of the raw products by film distillation without interruptions. After the film distillation the product is rectified on a column. The isomeric. mixture of the aminomethylaminopropylmorbornanes is a colorless liquid which boils at 12 mm Hg at to 15 1C.. The compounds are miscible with water at room temperatureinv any proportion, the elementary analysis confirms the composition C l-l N t The mixtures of the isomeric diamines of the invention according to the formulae land 11 are valuable compounds and can be used, for. example, as hardeners for epoxy resins or can be further processed afterconversion into the corresponding di-isocyanates to polyurethanes. In particular they can be transformed,,optionally together with further diamines by polycondensation with one or several aliphatic and/or cycloaliphatic and/or aromatic dicarboxylic acids directly into polyamides, which are distinguished by transparency and high second order transition temperatures and are especially suitable for treatment by injection molding.

In the preparation of the polyamides of the invention further diamines may be added to the mixture of the bis-(aminomethyl)-2-ethylnorbornanes these being:

0. aliphatic diamines with 2 to 20 carbon atoms and cycloaliphatic diamines; above all compounds of the general formula NH; (CI-l z are suitable as aliphatic diamines, wherein m is an integer of from 2 to 12; the stereoisomeric 1,3- and 1,4-bisaminomethyl-cyclohexanes, trans-l ,2-bisaminomethyl-cyclo-butane-cyclopentane and -cyclohexane are suitable as cyclo-aliphatic diamines. Especially suitable are ethylene diamine, hexamethylene diamine and 2-methyl-pentamethylene diamine.

d. aromatic diamines with 6 to 20, preferably 6 to 15' carbon atoms, above all mononuclear diamines of the benzene series, 4,4'-, 3,4'- and 3,3'-diamino-diphenyl and other diamino-diphenyls, diamino-diphenylmethanes, diamino-diphenyl ethers and diaminodiphenyl-sulfones, especially mand p-phenylene diamines. e. aromatic-aliphatic diamines with 7 to 20 carbon atoms and those of the general formula wherein R signifies a simple chemical bond or identical or different alkylene groups with l to 8 carbon atoms and Ar is a bivalent aromatic, optionally alkylsubstituted radical, for example mand p-xylylenediamine, 2,5-dimethyl-p-xylylene-diamine and 2,4- dimethyl-m-xylylene-diamine.

Mixtures of the diamines named in c) to e) can also be used. The maximum quantity of diamines, which can be incorporated by condensation without the polyamide losing its transparency, depends on the number of the diamines added and on their nature.

Aliphaticdiamines with branched carbon structure, as wellasdiarnines of which the carbon structure contains oneor several cycloaliphatic radicals, can be incorporated by condensation in greater quantity than those with straight-chain or aromatic carbon structure. Furthermore, a mixture of various diamines can be incorporated by condensation in greater quantity than a single diamine.

In general it is possible to add up to 80 mol-%, preferably up to 50 mol-% (calculated on the total diamine mixture), of the diamines named in (c) to (e), without the polyamide losing its transparency.

Suitable dicarboxylic acids are aliphatic, cycloaliphatic and aromatic dicarboxylic acids. As aliphatic dicarboxylic acids preferably acids with 2 to 20 carbon atoms are used and more preferably there are used compounds of the general formula HOOC (CH2)n COOI-I,

in which n is 0 or an integer from 1 to 10. Cycloalipahtic dicarboxylic acids which are preferably used are the stereoisomeric l,3-cyclopentanedicarboxylic acids, 1,3- and l,4-cyclohexanedicarboxylic acids and 4,4- dicyclohexyl-dicarboxylic acid. Especially suitable is adipic acid.

As aromatic dicarboxylic acids those with 7 to 20, preferably 8 to carbon atoms can be used, above all mononuclear dicarboxylic acids of the benzene series. Terephthalic acid and isophthalic acid are especially suitable. Further advantageous examples are 3,5- pyridinedicarboxylic acid, 1,4-, 1,5- and other naphthalene-dicarboxylic acids, 4,4'-diphenyl-dicarboxylic acid, diphenylsulfonedicarboxylic acids and benzophenonedicarboxylic acids.

As amino-carboxylic acids those with 2 to carbon atoms can be added, above all compounds with the general formula NI-I2 (CH2)p Coon (p= 1 to 11 especially amino-pivalic acids, e-amino-caproic acid and w-aminododecanoic acid.

Also aromatic or aliphatic-aromatic carboxylic acids of the formula NH R Ar COOI-I, wherein R is a simple chemical bond or an alkylene group with l to 8 carbon atoms and Ar is a bivalent, aromatic radical, which may be substituted by alkyl; mand p-amino-benzoic acids are especially preferred.

Mixtures of two or more of the dicarboxylic or amino carboxylic acids named can be also used.

The maximum quantity of amino-carboxylic acids, which can be incorporated by condensation without the polyamide losing its transparency depends on the number of amino-carboxylic acids added and their nature.

Aliphatic amino-carboxylic acids with branched carbon structure and also amino-carboxylic acids, of which the carbon structure contains one or several cycloaliphatic radicals can be incorporated by condensation in greater quantity than those with straight-chain or aromatic carbon structure. Furthermore, a mixture of various amino-carboxylic acids can be incorporated by condensation in greater quantity than an individual aminocarboxylic acid.

In general it is possible to add up to 70 per cent by weight, preferably up to 50 per cent by weight (calculated on the total mixture of the starting materials) of amino-carboxylic acids, without the polyamide losing its transparency.

amino- The polyamides of the invention can be prepared in the known way by melt condensation.

The diamine mixture and the dicarboxylic acid(s) in the stoichiometric quantities or in approximately stoichiometric quantities are put in an autoclave with stirrer possibly with the addition of water and/or acetic acid, or also the salt(s) of the diamine(s) and the dicarboxylic acid(s) and optionally an addition of aminocarboxylic acids(s) or its/their lactams, the mixture is melted, the steam is drawn off after some time, the mixture is stirred for some time in an inert gas stream and then condensed further in the vacuum, until the desired molecular weight is obtained.

The reduced specific viscosities of the polyamides should be between 0.8 dl/g and 3 dl/g (measured with solutions of l g of polyamide in 100 ml of phenoltetrachlorethane (3+2 parts by weight) at 25C), preferably between 1 dl/g and 2 dl/g.

In the melt condensation also amide-forming derivatives of the starting materials can be used; ie. in place of the dicarboxylic acids their esters or amides, in place of the diamines their amides or isocyanates, or in place of the amino-carboxylic acids their lactams.

A further mode of preparing the polyamides is to react the diamine mixture with dicarboxylic acid halides according to the process of interfacial or solvent condensation.

The polyamides of the invention are transparent and possess relatively high second order transition temperatures. The various components of the diamine mixture influence the properties of the polyamides in such a way that no crystallization takes place. On the other hand, the individual components of this diamine mixture, astonishingly, do not have the undesired effect of reducing the second order transition temperatures of the polyamides of the invention to too great an extent.

Some of the polyamides of the invention, become slightly cloudy by weak crystallization when they are cooled slowly from the melt. However, transparent molded articles are also obtained from them when they are cooled quickly to temperatures of below the glass temperature after the thermoplastic shaping has taken place, for example by injection molding with the aid of injection molding machines into cold forms.

The following Examples illustrate the invention Preparation of the mixture of isomeric aminomethylaminopropylnorbornanes EXAMPLE 1 A solution of 400 g (3.21 111018) of ethylidene norbornene in 800 ml of benzene, to which 0.2 mol of rhodium (III) octanoate had been added, was reacted in a 2-l-autoclave for 1 hour at to C with synthesis gas at a pressure of 450 atmospheres gauge. After cooling and withdrawing from the autoclave, the benzene was distilled off from the reaction solution in the falling-film evaporator at mm Hg and 80C jacket temperature.

The residue was again distilled at C jacket temperature and 3 to 5 mm Hg over the falling-film evaporator. 430 g 74.4% of the theor etical amount of the doubly formylated ethylnorbornane was passed over.

EXAMPLE 2 The repetition of example 1 with 400 g of vinylnorborne instead of ethylidene norbornene yielded under the same conditions 456 g 79 of the theoretical amount of doubly formylated ethylnorbornane.

The gaschromatographic analysis showed that there was no noticeable difference in the composition of the products which had formed from vinyl norbornene (Example 2) or ethylidene norbomene (Example 1) EXAMPLE 3 A high pressure vessel of 2 1 content was loaded with 204 g (12 mols) of ammonia, 200 ml of tetrahydrofurane and g of Raney-Nickel. Hydrogen was forced in up to a pressure of approx. 100 atmospheres gauge and the mixture was heated to 135C. When this temperature was reached hydrogen was forced in and a total pressure of 280 atmospheres gauge was set. Over a high pressure dosage pump 270 g (1.5 mols) of bisformylethylnorbornane mixture obtained according to Example 1 were pumped into the reaction vessel within 1 hour. The mixture was left to react for minutes and then cooled immediately. After cooling and releasing pressure of the excess hydrogen the product taken from the reaction vessel was filtered. Subsequently the remaining ammonia and the solvent were removed. The remaining raw product was distilled at approx. 1 mm Hg and 140C jacket temperature over a falling-film evaporator, the distillate obtained in this way was subsequently fractionated over a silver jacket column. The main fraction at bp 150 to 151C was obtained after short first runnings.

Yield: 210 g (1.15 mols), corresponding to 77% of 30 EXAMPLE 4 A high pressure vessel of 5 1 content was fed with 510 g (30 mols) of ammonia, 500 ml of isobutanol'and g of a catalyst, which contained 45% cobalt kieselguhr. After introducing hydrogen to increase the pressure to approx. 100 atmospheres the mixture was heated to 150C; when this temperature was reached a total pressure of 250 atmospheres was established by further introduction of hydrogen.

Using a high pressure dosage pump 540 g (3 mols) of bisformylethylnorbornane mixture obtained according to Example 2 were pumped into the reaction vessel within 1.5 hours. The mixture was left to react for a further 15 minutes and then cooled immediately The batch was worked up as described in Example 3.

The fractionated distillate yielded 431 g (2,37 mols) of a mixture of isomeric aminomethyl-aminopropylnorbornanes ie. 79% of the theoretical amount.

Preparation of the polyamides NH CH EXAMPLE 5 For the preparation of the salt 182.3 g of the mixture of bis-aminomethyl-2-ethylnorbornanes, 166.1 g of terephthalic acid and 2 1 of ethanol were heated for 1 hour to boiling, water was added slowly until a clear solution was obtained, the solvent was drawn off in the water jet vacuum and dried for 12 hours in the drying chamber.

For poly-condensation the salt was introduced into an autoclave, the air was displaced with nitrogen, the autoclave was evacuated and sealed. The salt was melted at 280C, stirred for 30 minutes at this temperature, the pressure was released in the course of 1 hour, nitrogen was passed through the apparatus and the melt stirred for 1 hour. Subsequently the pressure was reduced to 0.1 mm of mercury and the melt was stirred for 1 hour at 280C. The polyamide obtained was transparent and had a reduced specific viscosity of 1.4 dl/g and its second order transition temperature was 201C.

EXAMPLE 6 As described in Example 5 from 182.3 g of the diamine mixture and 166.1 g of isophthalic acid the salt was prepared and condensed at 280C.

The polyamide obtained was transparent and had a reduced specific viscosity of 1.3 dl/g and a second order transition temperature of 186C EXAMPLE 7 As described in Example 5, the salt was prepared from 182,3 g of the diamine mixture and 146.1 g of adipic acid and condensed at 280C. the polyamide obtained was transparent and had a reduced specific viscosity of 1.6 dl/ g and a second order transition temperature of 117C.

EXAMPLE 8 As described in Example 5, two salts were prepared separately from:

A: 182.3 g of the diamine mixture and 166.1 g of terephthalic acid;

B: 116.2 g of 2-methylpentamethylene diamine and 166.1 g of terephthalic acid. 200 g of salt A and 100 g of salt B are mixed together and, as described in Example 5, condensed at 280C The polyamide obtained was transparent and has a reduced specific viscosity of 1.1 dl/g and a second order transition temperature of 180C.

EXAMPLE 9 reduced specific viscosityof 1.6 dl/g and a second i order transition temperature of 171C.

What is claimed is:

1. A polyamide consisting essentially of the poly.- meric condensation product of a. a mixture of isomeric norbornanes of the formulae and 3 NH CH in which R is CH(CH )CH NH 0r b. a mixture of terephthalic acid with up to by weight, based on the total weight of reactants, of e-caprolactam, said polyamide having a reduced specific viscosity of 0.8 dl/g to 3 dl/g measured at a concentration of 1 gram of polyamide in ml of phenol-tetrachloroethane at a 3:2 weight ratio and at 25C. 2. A polyamide consisting essentially of the polymeric condensation product of a. a mixture of isomeric aminomethyl-aminopropyl norbornanes of the formulae aminopropyl norbomanes and component (b) is terephthalic acid.

7. A polyamide according to claim 2 wherein component (a) is said mixture of isomeric aminomethyl- 5 aminopropyl norbornanes and component (b) is isophthalic acid.

in which R is CH(CH )CH NH or CH CH CH NH or a mixture of said isomeric norbomanes and up to 80 mole percent of at least one branched chain aliphatic diamine of 2 to carbon atoms and b. at least one dicarboxylic acid which is an aromatic carbocyclic dicarboxylic acid of 8 to 20 carbon atoms, or an aliphatic dicarboxylic acid of 2 to 20 8. A polyamide according to claim 2 wherein component (a) is a mixture of said isomeric aminomethylaminopropyl norbornanes and component (b) is adipic 2O acid. I

9. A polyamide consisting essentially of the polycondensation product of a. a mixture of isomeric aminomethyl-aminopropyl norbornanes of the formulae 1 1 R2 NH ca 2 3 and 5 3 NH cu 2 2 4 carbon atoms, or a mixture of said dicarboxylic acid and up to 70% by weight, based on the total weight of reactants, of at least one aminocarboxylic acid of 2 to 20 carbon atoms, or a lactam of said aminocarboxylic acid, said polyamide having a reduced specific viscosity of 0.8 dl/g to 3 dl/g measured at a concentration of 1 gram of polyamide in 100 ml of phenol-tetrachloroethane at 3:2 weight ratio and at C.

3. A polyamide according to claim 2 wherein said aliphatic diamine is 2-methylpentamethylene diamine.

4. A polyamide according to claim 2 in which said dicarboxylic acid is terephthalic acid, isophthalic acid, adipic acid or a mixture of these acids.

5. A polyamide according to claim 2 wherein component (b) is a mixture of dicarboxylic acid and lactam and the lactam is e-caprolactam.

6. A polyamide according to claim 2 wherein component (a) is said mixture of isomeric aminomethylin which R is CH(CH )CH NH or CH CH CH NH and b. at least one aromatic carbocyclic dicarboxylic acid of 8 to 20 carbon atoms and from 0 to 70% by weight, based on the total weight of reactants, of an aminocarboxylic acid of 2 to 20 carbon atoms or a lactam thereof, said polyamide having a reduced specific viscosity of 0.8 dl/g to 3 dl/g measured at a concentration of 1 gram of polyamide in 100 ml of phenol-tetrachloroethane at a 3:2 weight ratio and at 25C. 10. A polyamide according to claim 9 wherein component (b) is terephthalic acid.

11. A polyamide according to claim 9 wherein component (b) is isophthalic acid.

12. A polyamide according to claim 9 wherein com- 50 ponent (b) is a mixture of terephthalic acid and e-caprolactam. 

1. A POLYAMIDE CONSISTING ESSENTIALLY OF THE POLYMERIC CONDENSATION PRODUCT OF A. A MIXTURE OF ISOMERIC NORBORNANES OF THE FORMULA
 2. A polyamide consisting essentially of the polymeric condensation product of a. a mixture of isomeric aminomethyl-aminopropyl norbornanes of the formulae
 3. A polyamide according to claim 2 wherein said aliphatic diamine is 2-methylpentamethylene diamine.
 4. A polyamide according to claim 2 in which said dicarboxylic acid is terephthalic acid, isophthalic acid, adipic acid or a mixture of these acids.
 5. A polyamide according to claim 2 wherein component (b) is a mixture of dicarboxylic acid and lactam and the lactam is epsilon -caprolactam.
 6. A polyamide according to claim 2 wherein component (a) is said mixture of isomeric aminomethyl-aminopropyl norbornanes and component (b) is terephthalic acid.
 7. A polyamide according to claim 2 wherein component (a) is said mixture of isomeric aminomethyl-aminopropyl norbornanes and component (b) is isophthalic acid.
 8. A polyamide according to claim 2 wherein component (a) is a mixture of said isomeric aminomethyl-aminopropyl norbornanes and component (b) is adipic acid.
 9. A polyamide consIsting essentially of the polycondensation product of a. a mixture of isomeric aminomethyl-aminopropyl norbornanes of the formulae
 10. A polyamide according to claim 9 wherein component (b) is terephthalic acid.
 11. A polyamide according to claim 9 wherein component (b) is isophthalic acid.
 12. A polyamide according to claim 9 wherein component (b) is a mixture of terephthalic acid and epsilon -caprolactam. 